CN101506929A - Method of preparing electrode, electrode composition for offset printing and plasma display screen - Google Patents
Method of preparing electrode, electrode composition for offset printing and plasma display screen Download PDFInfo
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- CN101506929A CN101506929A CNA2006800555441A CN200680055544A CN101506929A CN 101506929 A CN101506929 A CN 101506929A CN A2006800555441 A CNA2006800555441 A CN A2006800555441A CN 200680055544 A CN200680055544 A CN 200680055544A CN 101506929 A CN101506929 A CN 101506929A
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- composition
- electrode
- solvent
- organic binder
- binder bond
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
- H01J2211/20—Constructional details
- H01J2211/22—Electrodes
- H01J2211/225—Material of electrodes
Abstract
Disclosed are an electrode composition for offset printing, including conductive material, an organic binder, glass frit, and a solvent, a method of preparing an electrode using the same, and a plasma display panel including the electrode. The composition of the invention can exhibit superior transfer properties with the use of the organic binder having a glass transition temperature ranging from -5O DEG C to -5 DEG C. Further, when a fine electrode pattern is prepared on the front substrate and the rear substrate of the plasma display panel, it can be formed quickly and reproducibly.
Description
Technical field
Put it briefly, the present invention relates to be used for preparing the composition of electrode by lithographic printing, be specifically related to prebasal plate and the bus electrode of metacoxal plate and the preparation of addressing electrode of plasma display panel (PDP) (PDP), more specifically, relate to and be used for lithographic electrod composition, said composition comprises that electric conducting material, glass transition temperature are-50 ℃~-5 ℃ organic binder bond, glass dust and solvent.
Background technology
Recently, PDP, a kind of flat-panel monitor, in the time of with LCD and rear-projection TV keen competition, market-share growth is quick.
Specifically, be typically interchange (AC) type PDP, its formation comprises by transparency electrode (keeping electrode), bus electrode and is used to cover the front glass substrate that the dielectric layer of above-mentioned electrode is formed, and the back glass substrate with cellular construction relative with front glass substrate, this cellular construction is made up of addressing electrode, dielectric layer, barrier and fluorescent material, the mutually orthogonal arrangement of the electrode of above-mentioned two substrates.
By between the electrode of two substrates, applying voltage, send ultraviolet light thereby in the unit, produce discharge, ultraviolet light is used to excite the fluorescent material in the unit that is defined by barrier then, thereby produces luminescence phenomenon.In above-mentioned screen structure, the image that red, green and blue (RGB) the fluorescence combination of being sent by each unit obtains is identified in the back on the prebasal plate surface that is furnished with described electrode.In addition, in order to improve thus the picture quality (contrast) that shows, known method is to form black electrode between transparency electrode and bus electrode, makes bus electrode corresponding to the prebasal plate of display surface stop the identification from the back side.
Usually, electrode formation method comprises by silk screen printing the photosensitive electrode composition is coated on the whole surface of glass substrate, carries out photoetching only to expose and the required part of developing, and carries out calcine technology then, thereby makes electrode.
But it is disadvantageous using the conventional method of photoetching, because all parts comprise that unwanted part all is printed, these unwanted parts are removed by developing then, thereby have increased the waste of expensive material and increased manufacturing cost.And, because above-mentioned electrode has prolonged cycle process time by the preparation of series of process such as printing, drying, exposure, development and calcining undesirablely.
In addition, when silk screen printing, used metal and polyester net mask can become large deformation in time, thereby the thickness of printing becomes inhomogeneous.
In order to address the above problem, although proposed to use ink-jet printing process or film shifting process, owing to material cost height, technology amount reach shortcomings such as apparatus expensive greatly, limitation at present possesses skills.
For example, under the situation of ink jet printing, the printing ink that is used for ink jet printing will prepare with the conductive powder of the nano-scale of costliness, and this needs complicated preparation technology and high preparation cost.In addition, when preparing electrode, can not obtain the precision of fine pattern and enough thickness by ink jet printing.
In addition, under the situation of film shifting process, the photosensitive electrode composition is coated on the film, be transferred on the substrate, exposure is developed then, thereby form electrode pattern on substrate, adopting this method is in order to alleviate such as defectives such as the precision of limited screen mask and cycle process time are long, but has limitation on the waste degree that reduces expensive material.
Therefore, in order to overcome the problems referred to above, the present invention discloses and a kind ofly is applied to composition on the substrate by lithographic printing, so only print, drying and calcine technology, thereby number of processes is lacked than common process quantity, and only printing must partly thereby can repeatedly form the fine electrode pattern and not waste expensive material.
Summary of the invention
Technical scheme
Therefore, the present invention is directed to the problems referred to above that association area occurs and propose, and the purpose of this invention is to provide and a kind ofly can form the composition of fine pattern, thereby realize having high effect and it makes cheap PDP by lithographic printing.
Another purpose of the present invention provides electrode that uses the above-mentioned composition preparation and the PDP that comprises this electrode.
To achieve these goals, according to an aspect of the present invention, the invention provides a kind of lithographic composition that is used for, said composition comprises that electric conducting material, glass transition temperature are at-50 ℃~-5 ℃ organic binder bond, glass dust and solvent.
According to another aspect of the invention, the invention provides a kind of method for preparing electrode, this method comprises: a) prepare composition of the present invention, b) composition with a) middle preparation installs in the groove of gravure roll (gravure roll), c) groove of above-mentioned composition from gravure roll is transferred on the blanket roll of being made by silicon rubber (blanket roll), d) above-mentioned composition being transferred on the glass substrate from blanket roll, and e) dry and calcining is transferred to the composition on the glass substrate.
According to another aspect of the invention, the invention provides a kind of PDP that uses the electrode of method for preparing and comprise this electrode.
Disclosure of an invention
Below, with the present invention is described in detail.
According to the present invention, above-mentioned electrod composition is coated on the prebasal plate and metacoxal plate of PDP by lithographic printing, thereby can repeat to form fine pattern, and described pattern is subsequently by forming electrode such as heat treatments such as calcinings.Thereby, with reference to accompanying drawing, imprint lithography is described at first.
Imprint lithography of the present invention (offset process) was divided into for two steps, i.e. shifting process (offprocess) and typography (set process).Before shifting process, composition 14 of the present invention is loaded in the gravure roll 11 that is formed with the dark fine pattern with 50~150mm live width of 10~50mm, strike off technology for wiping the composition that overflows from gravure roll off with metallic spatula 12 then.Subsequently, carry out shifting process: blanket roll 15 is continued nip drum on the gravure roll 11 that composition is housed, make above-mentioned composition be transferred on the surface of the blanket roll 15 that forms by silicon rubber from the groove of gravure roll 11.
Then, carry out typography: blanket roll 15 nip drum on glass substrate 17 that will make by silicon rubber, with composition from the surface transfer of silicon rubber blanket to glass baseplate surface.
The present invention aims to provide and is applicable to lithographic electrod composition, thereby in imprint lithography, composition in the groove of gravure roll is transferred on the silicon rubber blanket equably and not produce pattern outstanding or lines are damaged, the composition that is transferred to subsequently on the silicon rubber blanket preferably is transferred on the glass substrate with the form of fine electrode pattern, and does not remain on the blanket.
At last, the present invention is used for lithographic electrod composition and comprises: a) electric conducting material of 50~95wt%, the b) organic binder bond of 1~20wt%, and c) glass dust of 1~20wt%, all the other are solvent.
The present invention is used for the used electric conducting material of lithographic electrod composition and works to improve conductance, and be at least a electric conducting material that is selected from the group that constitutes by gold, platinum, palladium, silver, copper, aluminium, nickel and their alloy, described electric conducting material is for having 0.1~3mm, the powder of preferred 0.5~2mm diameter.
The consumption of above-mentioned electric conducting material is 50~95wt%, and preferred 60~80wt%.When its consumption is lower than 50wt%, be difficult to the conductance that guarantees that electrode is enough.On the other hand, when its consumption surpasses 95wt%, when lithographic printing, can not normally carry out transfer printing process, and electrode becomes too thick.
In the present invention, as organic binder bond, glass transition temperature is that-50 ℃~-5 ℃ fluoropolymer resin is useful.When the glass transition temperature of above-mentioned organic binder bond is lower than-50 ℃, in shifting process and typography, forms a large amount of pattern projections, and use compressed air to be difficult to remove unnecessary impurity from the pattern that is transferred on the glass substrate.On the other hand, when described temperature surpassed-5 ℃, the composition that is transferred on the blanket did not have adhesiveness, thereby is difficult for being transferred on the glass substrate.
The example of organic binder bond comprise ethylenically unsaturated monomers and can with the copolymer of the another kind of ethylenically unsaturated monomers of its copolymerization, such as acrylic resin, the plain resin of aqueous fiber, polyvinyl alcohol resin, epoxy resin, melmac and polyvinyl butyral resin, they can be used alone or as a mixture.The consumption of this organic binder bond is 1~20wt%, and preferred 5~15wt%.When its consumption is lower than 1wt%, when printing and typography, is difficult to carry out transfer step, and is prone to sedimentation such as inorganic material such as silver powder.On the other hand, when its consumption surpassed 20wt%, calcining rear electrode surface produced many holes, and the conductance of electrode reduces.
Organic binder bond is preferably represented by following general formula 1, and is had interior weight average molecular weight of 1,000~200,000 scope and the acid number of 20~250mgKOH/g:
General formula 1
R
1: H or CH
3
R
2: alkyl (C
1~C
12), pi-allyl, aryl
In the present invention, solvent is used to dissolve organic binder bond, and has 100~300 ℃ boiling point, and preferred use only makes the primary alconol and the secondary alcohol of the slight swelling of silicon rubber blanket.
Described examples of solvents includes, but are not limited to: isopropyl alcohol, 2-Ethylhexyl Alcohol, methoxyl group amylalcohol, butyl cellosolve, ethoxy ethoxy ethanol, bu-toxyethoxy, methoxy propoxy propanol, glycerine, ethylene glycol, glycerine, Texanol, α-terpineol, kerosene, petroleum solvent and dihydro-terpineol.
In addition, in the present invention, can use to comprise that boiling point is the mixture of 100~150 ℃ first solvent and boiling point second solvent that is 200~300 ℃.At this moment, under the situation of second solvent of first solvent of 100~150 ℃ of boiling points and 200~300 ℃ of boiling points, their mixing ratio is preferably in the scope of 1:9~9:1.The reason of this scope is: if this mixing ratio is lower than 1:9, be difficult to composition is transferred on the substrate in typography; On the other hand, if this mixing ratio surpasses 9:1, in striking off technology, because very fast exsiccation, the composition that exists on the gravure roll can not normally be removed.
The present invention is used for increasing the glass dust of the adhesive force between electric conducting material and the substrate and mainly is made up of lead oxide, bismuth oxide or zinc oxide, and has 300~600 ℃ softening point and 200~500 ℃ glass transition temperature.Consider thickness, glass dust preferably has the diameter that is not more than 5mm.
The consumption of glass dust is 1~20wt%, and preferred 3~15wt%.When its consumption was lower than 1wt%, adhering between calcine technology rear electrode pattern and the electrode base board was not firm.On the other hand, when its consumption surpassed 20wt%, the relative quantity of electric conducting material or organic binder bond reduced, and causes the conductance of electrode pattern and mechanical strength low.
Except mentioned component, composition of the present invention can further comprise and is used to regulate the deliquescent plasticizer that dissolves in binder solution of organic binder bond.Easily the plasticizer that mixes with above-mentioned organic binder bond is used to regulate drying property.The example of plasticizer includes, but are not limited to: phthalic acid ester, adipate ester, phosphate, trimellitate, citrate, epoxy compounds, polyester, glycerine and monomer, oligomer and tripolymer with high boiling water soluble acrylic acid compounds.
In addition, in the present invention, can further comprise dispersant, viscosity stabiliser, defoamer and coupling agent when needing.
In addition, the invention provides a kind of method for preparing electrode.According to the present invention, the method for preparing transparency electrode comprises: a) prepare composition of the present invention, b) composition with a) middle preparation is loaded in the groove of gravure roll, c) groove of above-mentioned composition from gravure roll is transferred on the blanket roll that is formed by silicon rubber, d) above-mentioned composition is transferred on the glass substrate from blanket roll, and e) dry and calcining is transferred to the composition on the glass substrate, thereby forms required electrode.
And, the invention provides the PDP that comprises the electrode that uses said method formation.
Beneficial effect
The invention provides and be used for lithographic electrod composition, use this electrod composition to prepare the method for electrode and comprise the PDP of this electrode.According to the present invention,, be provided for lithographic electrod composition in order to realize PDP and manufacturing thereof.Use such composition, can be on the prebasal plate of PDP and metacoxal plate preparation electrode fast, guarantee sufficient conductance simultaneously and can repeat to form fine pattern.In addition, can only form electrode, therefore reduce the use of expensive conduction silver powder, thereby reduced material cost gradually, and then make low expense manufacturing PDP become possibility in required part.
Description of drawings
Fig. 1 is the schematic side view that the imprint lithography of composition of the present invention is used in expression.
11: gravure roll 12: metallic spatula
14: composition 15 of the present invention: blanket roll
17: glass substrate
Embodiment
Can better understanding be arranged to the present invention by following examples, these embodiment are used for illustrative purposes, should not be construed as limitation of the present invention.
Embodiment 1
Viscosity stabiliser malonic acid, the silver powder of 64wt% and the glass dust of 8.9wt% of Texanol solution, 0.17wt% of copolymer resin that 17.5wt% is comprised methacrylic acid-(methacrylic acid 2-Octyl Nitrite)-butyl acrylate of 60wt% mixes, stirs, use ceramic three-roller to mediate and disperse thereafter, the methoxy propoxy propanol that in the composition that obtains, adds 9.5wt% then again as retarder thinner to regulate its viscosity.
Embodiment 2
Texanol solution, the viscosity stabiliser malonic acid of 0.17wt%, the silver powder of 64wt% and the glass dust of 8.9wt% of the copolymer resin of the methacrylic acid that comprises 60wt%-(methacrylic acid 2-Octyl Nitrite)-butyl acrylate of 17.5wt% are mixed, stir, use ceramic three-roller to mediate and disperse thereafter, the butyl cellosolve that in the composition that obtains, adds 9.5wt% then again as retarder thinner to regulate its viscosity.
Embodiment 3
Texanol solution, the viscosity stabiliser malonic acid of 0.17wt%, the silver powder of 64wt% and the glass dust of 8.9wt% of the copolymer resin of the methacrylic acid that comprises 60wt%-(methacrylic acid 2-Octyl Nitrite)-butyl acrylate of 17.5wt% are mixed, stir, use ceramic three-roller to mediate and disperse thereafter, the ethoxy ethoxy ethanol that in the composition that obtains, adds 9.5wt% then again as retarder thinner to regulate its viscosity.
Embodiment 4
Butoxy ethanol solution, the viscosity stabiliser malonic acid of 0.17wt%, the silver powder of 64wt% and the glass dust of 8.9wt% of the copolymer resin of the methacrylic acid that comprises 60wt%-(methacrylic acid 2-Octyl Nitrite)-butyl acrylate of 17.5wt% are mixed, stir, use ceramic three-roller to mediate and disperse thereafter, the butyl cellosolve that in the composition that obtains, adds 9.5wt% then again as retarder thinner to regulate its viscosity.
Comparative Examples 1
The texanol solution of the methacrylic acid that comprises 60wt%-methylmethacrylate copolymer resin of 17.5wt%, the viscosity stabiliser malonic acid of 0.17wt%, the silver powder of 64wt% and the glass dust of 8.9wt% are mixed, stir, use ceramic three-roller to mediate and disperse thereafter, the dipropylene glycol methyl ether that in the composition that obtains, adds 9.5wt% then again as retarder thinner to regulate its viscosity.
In order to estimate, on glass substrate with dystectic 14cm * 14cm size, use offset press that each composition coating of embodiment 1~3 and Comparative Examples 1 is formed electrode pattern, the substrate that will scribble composition is then put into infrared band oven and is kept 10 minutes to be dried in 100 ℃.Thereafter, the transfer printing state behind the observation shifting process on blanket, the transfer printing state after the typography on substrate, and the residual condition of the composition on blanket.Then, aforesaid substrate was observed its pattern form and measured its resistance 560 ℃ of calcinings in 20 minutes.Its result provides in following table 1.
Evaluation criterion
1. shifting process
Excellent: pattern-free is outstanding and do not have a lines breakage
Very: slightly produce the outstanding and lines breakage of pattern
Difference: produce the outstanding and lines breakage of pattern in a large number
2. typography
Excellent: pattern-free is outstanding and do not have a lines breakage
Very: slightly produce the outstanding and lines breakage of pattern
Difference: produce the outstanding and lines breakage of pattern in a large number
3. residual on blanket after the typography
Excellent: noresidue
Very: small amount of residual
Difference: residual in a large number
4. the electrode shape after calcining
Excellent: top of electrodes is circle and bottom noresidue
Very: top of electrodes is that circle and bottom have residual
Difference: top of electrodes is that wedge angle and bottom have residual
Table 1
Estimate | Embodiment 1 | Embodiment 22 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 |
The glass transition temperature of copolymer resin (℃) | -15 | -15 | -15 | -15 | 100 |
Shifting process | ◎ | ○ | ◎ | ○ | ◎ |
Typography | ◎ | ◎ | ○ | ◎ | × |
Residual behind the shifting process on the blanket | ◎ | ◎ | ◎ | ○ | × |
Resistivity (μ Ω .cm) | 3.6 | 3.6 | 3.6 | 3.6 | 3.2 |
Calcining back thickness (μ m) | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
Calcining rear electrode shape | ◎ | ○ | ◎ | ○ | × |
(◎: excellent, zero: good, *: poor)
As shown in table 1, in embodiment 1~4, all assessment items all obtain good result.In Comparative Examples 1, be poor for the evaluation result of residual condition on typography, the blanket and calcining rear electrode shape.
Industrial usability
The present invention discloses and a kind ofly is applied to composition on the substrate by lithographic printing, can only print like this, drying and calcine technology, thereby number of processes lacks than common process quantity, thereby and only printing is essential partly can repeatedly form the fine electrode pattern and not waste expensive material.
Although for purposes of illustration, preferred implementation of the present invention is disclosed, it will be understood by those skilled in the art that under the situation of the scope and spirit of the present invention that do not deviate from the appended claims requirement, can carry out various modifications, increase and replacement.
Claims (11)
1, a kind ofly be used for lithographic electrod composition, comprise: a) electric conducting material, b) organic binder bond, and c) glass dust, and solvent, the glass transition temperature of wherein said organic binder bond is-50 ℃~-5 ℃.
2, composition as claimed in claim 1 comprises:
A) the described electric conducting material of 50~95wt%;
B) the described organic binder bond of 1~20wt%; And
C) the described glass dust of 1~20wt%, all the other are described solvent.
4, composition as claimed in claim 3, wherein said organic binder bond has 1,000~200, weight average molecular weight in 000 scope and the acid number of 20~250mgKOH/g.
5, composition as claimed in claim 1, wherein said solvent comprise at least a first solvent and at least a second solvent with 200~300 ℃ of boiling points with 100~150 ℃ of boiling points that mixes.
6, composition as claimed in claim 5, wherein said first solvent and described second solvent with 200~300 ℃ of boiling points with 100~150 ℃ of boiling points mixes with the mixing ratio of 1:9~9:1.
7, composition as claimed in claim 1, wherein said glass dust have 300~600 ℃ softening point and 200~500 ℃ glass transition temperature.
8, composition as claimed in claim 1, further comprise and being selected from by phthalic acid ester, adipate ester, phosphate, trimellitate, citrate, epoxy compounds, polyester, at least a plasticizer in the group of glycerine and the monomer with high boiling water soluble acrylic acid compounds, oligomer and tripolymer formation.
9, composition as claimed in claim 1 further comprises at least a auxiliary agent that is selected from the group that is made of dispersant, viscosity stabiliser, defoamer and coupling agent.
10, a kind of method for preparing electrode comprises:
A) any described composition in the preparation claim 1~9;
B) composition that makes in a) is loaded in the groove of gravure roll;
C) transfer to described composition on the blanket roll that forms by silicon rubber from the groove of gravure roll;
D) described composition is transferred on the glass substrate from blanket roll; And
E) dry and calcining is transferred to the composition on the glass substrate.
11, a kind of plasma display panel (PDP) comprises the electrode with the described method preparation of claim 10.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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KR1020060080623 | 2006-08-24 | ||
KR10-2006-0080623 | 2006-08-24 | ||
KR1020060080623A KR100800263B1 (en) | 2006-08-24 | 2006-08-24 | Electrode composition for offset print, method for preparing a electrode by the same and a plasma display panel using the same |
PCT/KR2006/005623 WO2008023864A1 (en) | 2006-08-24 | 2006-12-21 | Electrode composition for offset print, method for preparing a electrode by the same and a plasma display panel using the same |
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CN101506929A true CN101506929A (en) | 2009-08-12 |
CN101506929B CN101506929B (en) | 2012-01-18 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102456573A (en) * | 2010-10-22 | 2012-05-16 | 元太科技工业股份有限公司 | Manufacturing method for thin film transistor |
CN102486984A (en) * | 2010-12-01 | 2012-06-06 | 第一毛织株式会社 | Electrode composition of offset printing |
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US5334411A (en) * | 1993-01-11 | 1994-08-02 | E. I. Du Pont De Nemours And Company | Multilayer ceramic capacitor manufacturing process |
TW507500B (en) * | 2001-01-09 | 2002-10-21 | Sumitomo Rubber Ind | Electrode plate for plasma display panel and manufacturing method thereof |
CN1545111A (en) * | 2003-11-26 | 2004-11-10 | 廖晓华 | Conductive pulp for terminal electrode of chip capacitor |
CN1290121C (en) * | 2005-03-08 | 2006-12-13 | 东南大学 | Photosensitive silver slurry for concentration electrode and method for preparing same |
CN1329926C (en) * | 2005-05-13 | 2007-08-01 | 范琳 | Electrode thick liquid without lead and silver and mfg. method thereof |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102456573A (en) * | 2010-10-22 | 2012-05-16 | 元太科技工业股份有限公司 | Manufacturing method for thin film transistor |
CN102486984A (en) * | 2010-12-01 | 2012-06-06 | 第一毛织株式会社 | Electrode composition of offset printing |
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